JP2002528610A - Shear-thinning ethylene / α-olefin interpolymer and process for producing them - Google Patents

Abstract

Shear-thinning ethylene/±-olefin and ethylene/±-olefin/diene monomer interpolymers that do not include a traditional branch-inducing monomer such as norbornadiene are prepared at an elevated temperature in an atmosphere that has little or no hydrogen using a constrained geometry complex catalyst and an activating cocatalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

BACKGROUND OF THE INVENTION The present invention relates to a shear thinning ethylene / α-olefin (EAO) interpolymer
It is about. This interpolymer has a low processing rheology ratio (PRR).
It has at least 4 and indicates that long chain branching (LCB) is present. This
Is an ordinary LCB monomer such as norbornadiene (NBD)
Such a PRR can be realized even without the above. This alpha-olefin (α-ole
The fin) suitably has 3 to 20 carbon atoms (C₃~ C₂₀Including) and preferred
Or propylene (C₃), 1-butene, 1-hexene or 1-octene (C ₈ ). The interpolymer is a diene (diolefin) monomer, preferably
Or non-conjugated diene monomers such as 5-ethylenediene-2-norbornene (ENB)
Desirably. EAO interpolymers containing this diene are generally
Is referred to as "EAODM interpolymer". EAO and EAODM
Interpolymers are collectively referred to as "EAO (D) M interpolymers."
You. The present invention also provides a method of making such an interpolymer,
-Compositions comprising polymers and forms from such interpolymers or compositions
An article of manufacture comprising at least one part or part formed.

SUMMARY OF THE INVENTION A first aspect of the present invention is a shear thinning EAO (D) M interpolymer,
The interpolymer has polymerized ethylene, at least one α-olefin monomer, and, optionally, at least one diene monomer therein;
Is at least 4. This interpolymer is ethylene (
C ₂ ) content of 20 to 95 weight percent (wt%), α-olefin content of 8
0 to 5 wt% and the α-olefin is a C _3-20 α-olefin, optionally with a diene monomer content ranging from greater than 0 to 25 wt%, all percentages being based on interpolymer weight. And 100 in total
wt%. The EAO (D) M interpolymer achieves such PRR without NBD or other conventional LCB monomers.

[0003] Interpolymer viscosities typically range from 0.1 to 100 radians per second (rad / sec) under a nitrogen atmosphere using a dynamic mechanical spectrometer such as RMS-800 or ARES from Rheometrics. At 190 ° C. in poise (dyne-sec / square centimeter (d-sec / cm ² )). 0.
The viscosities at 1 rad / sec and 100 rad / sec can be expressed as V _0.1 and V ₁₀₀ , respectively, and the ratio of the two is referred to as RR, V _0.1 / V
Expressed as V _100. RRR = RR + [3.82-interpolymer Mooney viscosity (ML _{1 + 4} at 125 ° C.) × 0.3.

[0004] A second aspect of the present invention is a process for the preparation of the EAO (D) M interpolymer of the first aspect, which comprises under conditions sufficient to achieve at least 60 weight percent ethylene conversion. , Ethylene, at least one α-olefin monomer and optionally at least one diene monomer with a catalyst and an activating catalyst, the conditions comprising at least 70 ° C, more preferably at least 80 ° C.
C., and optionally in the presence of an effective amount of hydrogen, the effective amount being an amount sufficient to maintain the interpolymer PRR at least 4.
The catalyst is at least one geometrically constrained metal composite. _C3-20 α-olefin monomers are suitable as α-olefin monomers. This method is particularly suitable for EAO (D) M where the diene or polyene is ENB, 1,4-hexadiene or a similar non-conjugated diene or conjugated diene such as 1,3-pentadiene.
Useful for solution polymerization of interpolymers. This diene has ENB or 7
-Methyl-1,6-octadiene is preferred. As in the first embodiment, this interpolymer PRR is realized without the usual LCB monomers.

A third aspect of the present invention is a polymer blend composition comprising the interpolymer of the first aspect and an amount of a crystalline polyolefin resin, desirably a propylene polymer or copolymer, preferably polypropylene (PP). The interpolymer is desirably present in an amount less than 50 parts by weight (pbw), and the crystalline polyolefin resin is desirably present in an amount exceeding 50 pbw. When the interpolymer is an EAODM interpolymer, the polymer blend is referred to as a thermoplastic elastomer or TPE. When the interpolymer is an EAO interpolymer, the polymer blend is referred to as a thermoplastic polyolefin or TPO.

[0006] A fourth aspect of the present invention is directed to an interpolymer of the first aspect that is at least partially cross-linked (also referred to as cure or vulcanization) and again a crystalline propylene polymer or copolymer, preferably a PP. It is a polymer blend composition containing a polyoffefin resin. This interpolymer is 40 to 90 pb
w, and the crystalline polyolefin resin is 60 to 10 p
Desirably, it is present in an amount of bw. Preferably, the interpolymer is sufficiently crosslinked to provide a gel content of at least 70% based on the weight of the interpolymer.

In both the third and fourth aspects, the amounts of the interpolymer and the crystalline polyolefin resin are based on the total weight of the interpolymer and the crystalline polymer and add up to 100 pbw.

DESCRIPTION OF THE PREFERRED EMBODIMENTS In this specification, everything relating to the Periodic Table of the Elements is described in CRC Press, Inc. ,
Reference is made to the periodic table issued in 1989 with copyright. Also, any references to groups or groups are groups or groups as reflected in this Periodic Table of the Elements using the numbered groups in the IUPAC system.

The pure inventive EAO (D) M interpolymer has three different properties
. The first is at least four PRRs. This PRR ranges from 4 to 350
Desirably, from 4 to 250 is preferred, and from 8 to 150 is most preferred.
Second, Mooney viscosity or MV (ML_{1 + 4}@ 125 ° C, ASTM D164
6-94) is in the range of 0.5 to 200, preferably 5 to 120, more preferably
Is from 10 to 85. Third, the molecular weight distribution (MWD or MWD)_w/ M _n ) Ranges from 2 to 5, preferably 2.0 to 3.8, and more preferably 2
. 2 to 3.2. Given these characteristics, the preferred EAO (D
) The M interpolymer has a MWD of at least 2.5 and a PRR of at least 8.
You. Preferred EAODM interpolymers have a MWD of at least 2.2, a low MV
It has at least 15 and at least 10 PRR. EAO is C₂/ C₈(EO)
When a copolymer, the MWD is at least 2.3, the MV is at least 5,
The PRR is preferably greater than 4.

In the solution polymerization method, a known and superior method for controlling the molecular weight is a chain termination reaction by heat termination, hydrogen termination, or both. It is believed that thermal termination results in chain ends with reactive vinyl groups, while hydrogen termination results in non-reactive saturated end groups. In most cases, thermal shutdown will compete with hydrogen shutdown. It is also believed that the formation of reactive vinyl end groups under the process conditions detailed above, and their subsequent reinsertion into the increased polymer backbone, results in a polymer product with an in-situ generated LCB. . Thus, a combination of reaction conditions that favors the formation of reactive vinyl end groups, such as little or no hydrogen and a high polymerization temperature, incorporates the reactive vinyl end groups and then incorporates the reactive vinyl end groups. It is believed to be advantageous to cause an increase in LCB concentration as represented by an increase in PRR.

The EAO (D) M interpolymer of the present invention has C₂, At least one C _3-20 α-olefin (ethylenically unsaturated) monomer and optionally C_{4 ~ 40} Polymerizes diene monomers (other than NBD or other common LCB monomers)
Have. The α-olefin is either an aliphatic or an aromatic compound.
Styrene, p-methylstyrene, cyclobutene, cyclopentene
And the 5th and 6th positions are C_1-20Norbornene substituted with hydrocarbyl groups
Can contain vinylic unsaturated or cyclic compounds such as norbornene containing
is there. This α-olefin has C_3-20It is preferably an aliphatic compound,
C_3-16More preferably, it is an aliphatic compound. Preferred ethylenically unsaturated
Monomers include 4-vinylcyclohexene, vinylcyclohexane, and C_{3 -10} Aliphatic α-olefins (especially ethylene, propylene, isobutylene, 1-
Butene, 1-pentene, 1-hexene, 3-methyl-1-pentene, 4-methyl
-1-pentene, 1-octene, 1-decene and 1-dodecene).
More preferred C_3-10Aliphatic α-olefins include propylene, 1-butene, 1
Selected from the group consisting of -hexene and 1-octene.

[0012] The inventive interpolymers, 95 wt% of _{C 2} content of 20, 93 wt% and more preferably from 30, most preferably 90 wt% from 35. The interpolymer also contains at least one alpha olefin other than C ₂ from 5 to 80 wt.
%, More preferably from 7 to 70 wt%, most preferably from 10 to 65 wt%. Finally, the interpolymer can include a non-conjugated diene. When the interpolymer comprises a non-conjugated diene, the non-conjugated diene content is preferably above 0 to 25 wt% or more, more preferably above 0 and 15 wt%.
%, Most preferably above 0 and up to 10 wt%. All percentages are based on interpolymer weight. If desired, more than one diene, such as 1,4-hexadiene and ENB, can be incorporated simultaneously, such that the total diene incorporation is within the limits specified above.

The C _4-40 diolefin or diene monomer is preferably a non-conjugated diolefin which is usually used as a polymerization site for crosslinking. The non-conjugated diolefin can be a _C6-15 linear, branched or cyclic hydrocarbon diene. Examples of non-conjugated dienes include linear non-cyclic dienes such as 1,4-hexadiene and 1,5-heptadiene, 5-methyl-1,4-hexadiene, 2-methyl-1,5-hexadiene, 6-methyl-1. , 5-heptadiene, 7-methyl-1,6-octadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-
Branched acyclic dienes such as octadiene, 5,7-dimethyl-1,7-octadiene, 1,9-decadiene and isomer mixtures of dihydromyrcene;
Monocyclic alicyclic dienes such as cyclohexadiene, 1,5-cyclooctadiene and 1,5-cyclododecadiene, polycyclic alicyclic fused ring dienes and linked ring dienes such as tetrahydroindene and methyltetrahydroindene, alkenyl, alkylidene, Cycloalkenyl and 5-methylene-2-norbornene (MNB), EN
B, 5-vinyl-2-norbornene, 5-propenyl-2-norbornene, 5-
Cycloalkylidene norbornene such as isopropylidene-2-norbornene, 5- (4-cyclopentenyl) -2-norbornene and 5-cyclohexylidene-2-norbornene. The diene is preferably a non-conjugated diene selected from the group consisting of ENB and 1,4-hexadiene, 7-methyl-1,6-octadiene, more preferably ENB. However, this diolefin is 1,
3-pentadiene, 1,3-butadiene, 2-methyl-1,3-butadiene, 4
It can be a conjugated diene selected from the group consisting of -methyl-1,3-pentadiene or 1,3-cyclopentadiene. The EAODM diene monomer content, whether or not containing conjugated dienes, non-conjugated dienes or both, is within the non-conjugated diene limits specified above.

Preferred interpolymers are generally substantially free of diene monomers that induce LCB, but are cost-acceptable and have unacceptable levels of desired interpolymer properties such as processability, tensile strength and elongation. If not, it is possible to include such monomers. Such diene monomers include dicyclopentadiene, NBD, methylnorbornadiene, vinyl-norbornene,
, 6-octadiene, 1,7-octadiene, and 1,9-decadiene. When adding such a monomer, based on the weight of the interpolymer,
It is added in an amount ranging from above 0 to 3 wt%, more preferably from above 0 to 2 wt%.

Various articles or products or components or components thereof can be manufactured using the interpolymers of the present invention. For purposes of illustration only, and not by way of limitation, such articles may include wire and cable components, electrical insulators, belts, hoses, tubes, gaskets, membranes, moldings, extruded parts, automotive parts, adhesives, tires. And sidewalls of the tire.

Although the interpolymer of the present invention can be used as it is, it is preferable to find use as a component of a compound. The compound is generally at least selected from the group consisting of fillers, fibers, plasticizers, oils, colorants, stabilizers, foaming agents, set retarders, set accelerators, crosslinkers and other common additives. It comprises at least one polymer mixed with one additive. Preferably, the interpolymers of the present invention include at least a portion of the polymer content of such compounds.

[0017] Interpolymers, and compounds containing such interpolymers, can be converted to final products by one of several conventional methods and equipment. Illustrative methods include extrusion, calendering, injection molding, compression molding, spinning, and other common thermoplastic methods.

The interpolymer of the present invention also serves as a base polymer in making a graft polymer. Unsaturated organic compounds containing at least one ethylenic unsaturation (at least one double bond) and grafting to the interpolymers of the present invention include:
It can be used to modify such an interpolymer. Exemplary unsaturated compounds include vinyl ethers, vinyl substituted heterocyclic compounds, vinyl oxazolines, vinyl amines, vinyl epoxides, unsaturated epoxy compounds, unsaturated carboxylic acids and anhydrides, ethers, amines, amides, succinimides or the like. Includes esters of acids. Representative compounds include maleic acid, fumaric acid,
Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, α-methyl crotonic acid and cinnamic acid and their anhydrides, ester or ether derivatives, vinyl-substituted alkylphenols and glycidyl methacrylates are included. Suitable unsaturated amines include at least one double bond and at least one amine group (
Aliphatic and heterocyclic organic nitrogen compounds containing at least one primary, secondary, or tertiary amine) are included. Maleic anhydride is a preferred unsaturated organic compound. Grafted interpolymers can be used for some applications, only one example being a component of an oily compound. The use of grafted EPDM interpolymers in oily compositions, the methods used to prepare such grafted interpolymers and various graft moieties is described in WO 97/329.
46 (US Priority Document 60/013052, March 8, 1996, and 19
No. 60/024913, Aug. 30, 1996, the relevant teachings of which or the corresponding US application is incorporated herein by reference.

As mentioned in the third and fourth aspects, the interpolymer comprises TPE, TPE
It can be used for the production of PO or TPV. There are several references for the general operation of TPE production. One such reference is 1
EP 751182, published January 2, 997, the relevant teachings of which are incorporated herein by reference.

The olefins that can be used in the production of the crystalline polyolefin resin include 1
One or more ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 2-methyl-1-propene, 3-methyl-1-
Pentene, and 4-methyl-1-pentene. Preferably, the crystalline polyolefin is a PP homopolymer or copolymer of propylene having an α-olefin such as ethylene, 1-butene, 1-hexene, or 4-methyl-1-pentene or a blend of homopolymer and copolymer. The preferred α-olefin is ethylene. This crystalline polyolefin can be prepared by an appropriate method such as random polymerization or block polymerization. Various forms, such as isotactic and syndiotactic, can also be used. Generally commercially available crystalline resins include PP homopolymer and propylene / ethylene (P / E) copolymer resins. Certain olefin copolymer resins, especially propylene copolymers such as P / E copolymers, can be referred to as "semi-crystalline" resins. "Crystalline" as used to describe a polyolefin resin has a broad enough meaning to include such semi-crystalline resins. This crystalline resin can be used alone or in combination.

The preparation of PP homopolymers and P / E copolymers is also described in US Pat.
Includes the use of a Ziegler catalyst such as titanium trichloride in combination with aluminum diethyl monochloride, as described by Cecchin at 60. Polymerization processes used to produce PP include about 50-90 ° C.
Includes slurry methods performed at 5 to 1.5 MPa (5 to 15 atm), and both gas phase and liquid monomer methods that require special care to remove amorphous polymer. Ethylene can be added to the reaction to form polypropylene with the ethylene block. PP resins can also be prepared by using any of a variety of metallocene, single site and constrained vaporization catalysts with related methods.

Several patents and applications disclose geometrically constrained metal composites and methods of making them. A non-exhaustive example is EP-A-416.
815 (US Patent Application No. 545403, filed July 3, 1990), EP-A
-468651 (U.S. Patent Application No. 544718, filed July 3, 1991);
EP-A-514828 (U.S. Patent Application No. 702475, May 20, 1991)
JP-A-520732 (U.S. Patent Application No. 876268, 1992).
(Filed May 1, 1998) and WO 93/19104 (US Patent Application No. 8003, 1
(Filed on January 21, 993) and US-A-5055438, US-A-505.
7475, US-A-5096867, US-A-5064802, US-A-
US Pat. No. 5,132,380, US Pat. No. 5,470,993, US Pat.
-A-5624878, WO 95/00526, and US Provisional Application 60-005.
913 are included. U.S. Patent Application No. 592756, filed January 26, 1996,
WO95 / 14024, WO98 / 27103 (based on US provisional application 60/034817 on December 19, 1996, 08/949505 on October 14, 1997) and PCT / US97 / 07252 (filed on April 30, 1997). Disclose various substituted indenyl-containing metal complexes. All relevant teachings of said patents and publications or corresponding U.S. patent applications are incorporated herein by reference.

Generally, metal complexes suitable for use include additional polymerizable compounds, particularly 3-10 of the Periodic Table of the Elements that can be activated to polymerize olefins with the activators of the present invention. Group metal complexes. Examples include the expression

[0024]

Embedded image

Embedded image wherein the M ^* is Ni (II) or P
X 'is halo, hydrocarbyl, or hydrocarbyloxy, Ar ^* is an aryl group, especially 2,6-diisopropylphenyl or aniline group, and CT-CT is 1,2-ethanediyl, , 3-butanediyl or a fused ring system in which the two T groups are both 1,8-naphtanediyl groups, and A ⁻ is the anionic component of the charge separation activator described above.

[0026] Similar conjugates described above are also described in Am. Chem. Soc. 118, 267-
268 (1996) and J.M. Am. Chem. Soc. , 117, 6414-
6415 (1995). Brookhart, et al. And active polymerization catalysts, especially for the polymerization of α-olefins, alone or in combination with polar comonomers such as vinyl chloride, alkyl acrylates and alkyl methacrylates.

Additional conjugates include groups 3, 4 or lanthanide metals comprising one to three pi-bonded anionic or neutral ligands, and cyclic or acyclic delocalized pi-bonded anions. It can be an ionic ligand group. The term “π bond” means that the ligand group binds to the transition metal by sharing a partially delocalized π bond electron.

Each atom of the delocalized π-bonded group is independently a hydrogen, a halogen, a hydrocarbyl, a halohydrocarbyl, a hydrocarbyloxy, a hydrocarbyl sulfide, a dihydrocarbylamino, and a hydrocarbyl wherein the metalloid is selected from group 14 of the periodic table of the elements. The hydrocarbyl, halohydrocarbyl, hydrocarbyloxy, hydrocarbyl sulfide, dihydrocarbylamino, and hydrocarbyl-substituted metalloid radicals can be further substituted with a radical selected from the group consisting of substituted metalloid radicals. Substituted with a group 15 or 16 hetero atom. The scope of the term "hydrocarbyl" includes C _1-20 linear,
Includes branched and cyclic alkyl radicals, _C6-20 aromatic radicals, _C7-20 alkyl substituted aromatic radicals, and _C7-20 allyl substituted alkyl radicals. Further, two or more such radicals can form together a fused ring system, including a partially or fully hydrogenated fused ring system, or form a metallocycle with a metal. It is possible. Suitable hydrocarbyl-substituted organic metalloid radicals include Group 14, 1, 2, and 3-substituted organic metalloid radicals, where each hydrocarbyl group contains from 1 to 20 carbon atoms. Examples of suitable hydrocarbyl-substituted organic metalloid free radicals include trimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl, triphenylgermyl, and trimethylgermyl groups. Examples of moieties containing Group 15 or 16 heteroatoms include amine, phosphine, ether or thioether moieties or divalent derivatives thereof, such as transition metals or lanthanide metals, and amides having attached hydrocarbyl or hydrocarbyl substituted metalloid containing groups,
Includes phosphide, ether or thioether groups.

Examples of such π-bonded anionic ligand groups include conjugated or non-conjugated, cyclic or acyclic dienyl groups, allyl groups, boratabenzene groups, and arene groups. Examples of suitable anionic delocalized π-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl , hexa hydro anthracenyl, decahydro-anthracenyl group and s- indacenyl, and their _{C 1 to 10 hydrocarbyl-substituted, C 1 to 10} hydrocarbyloxy substituted, di _{(C 1 to 10} hydrocarbyl) amino-substituted, or tri ( It includes C _{1 to 10} hydrocarbyl) silyl-substituted derivatives. Preferred anion delocalized π-bonding groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, s-indacenyl, 2-methyl-s-indacenyl, and tetrahydroindenyl.

Boratabenzene is an anionic ligand that is a benzene analog containing boron. These are already known in the art and are described in Herberich, et al. Organometallics, 1995, 14, 1, 471-480.

A first preferred geometrically constrained catalyst corresponds to Formula II:

[0032]

Embedded image

Wherein M is titanium, zirconium or hafnium in the +2, +3 or +4 formative oxidation state, and A ′ is at least 2-position hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydrocarbyl A substituted indenyl group substituted with a group selected from: silyl, germyl and mixtures thereof, said group containing up to 40 non-hydrogen atoms, wherein said A 'is further substituted with M by a divalent Z group. Covalently linked, Z is a divalent moiety linked to A 'and M by a sigma bond, wherein Z comprises boron or a member of group 14 of the periodic table of the elements and also forms nitrogen, phosphorus, sulfur or oxygen Including
X is an anion or dianion ligand group of up to 60 atoms other than the ligand species which is a cyclic delocalized π-bonded ligand group, and X ′ is independently 2 at each occurrence.
A neutral Lewis base coordination compound having up to 0 atoms, wherein p is 0, 1 or 2
And 2 less than the formal oxidation state of M, except that when X is a dianionic ligand group, p is 1 and q is 0, 1 or 2.

[0034] Additionally preferred catalysts or coordination complexes are described in WO 98/2710, already incorporated by reference.
3 and PCT / US97 / 07252. PCT / US97 /
In particular, on page 4, line 34 to page 16, line 36 of 07252, the following formula I
Preferred coordination complexes, such as those regenerated like II, IVA and IVB, are disclosed. Formula I below is a variant of Formula II on page 7 of PCT / US97 / 07252.

Preferably, the catalyst comprises a metal coordination complex corresponding to Formula I,

[0036]

Embedded image

Wherein M is defined as in Formula II above, and R ′ and R ″ are each independently at each occurrence hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbyl Silylamino, di (hydrocarbyl) amino, hydrocarbyleneamino, di (hydrocarbyl) phosphino, hydrocarbylene-phosphino, hydrocarbyl sulfide, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl, hydrocarbylsilyl Amino substituted hydrocarbyl, di (hydrocarbyl) amino substituted hydrocarbyl, hydrocarbylene amino substituted hydrocarbyl, di (hydrocarbyl) phosphino substituted Hydrocarbyl, hydrocarbylene-phosphino substituted hydrocarbyl,
Or a hydrocarbyl sulfide-substituted hydrocarbyl, wherein R ′ or R
The '' group has up to 40 non-hydrogen atoms, optionally two or more of the above groups are capable of forming a divalent derivative together, and R '''' together with the rest of the metal complex Is a divalent hydrocarbylene or substituted hydrocarbylene group,
"" Contains 1 to 30 non-hydrogen atoms, Z is a divalent moiety or a moiety containing one sigma bond and two neutral electron pairs capable of forming a coordination-covalent bond to M. Wherein Z comprises boron or a member of Group 14 of the Periodic Table of the Elements, and comprises nitrogen, phosphorus, sulfur or oxygen; X 'is a neutral coordination compound having up to 20 atoms independently at each occurrence, X'
'Is a divalent anionic ligand group having up to 60 atoms, and p is 0, 1, 2
Or 3, q is 0, 1 or 2, and r is 0 or 1.

The complex may be in the form of a solvent adduct, optionally in pure form, as an isolated crystal, or as a mixture with another complex, optionally in a solvent, in particular in an organic liquid. It is possible that the dimer or chelating agent is present in the form of a chelating derivative which is an organic substance such as ethylenediaminetetraacetic acid (EDTA).

In the metal complexes defined by formulas I and II, preferred X ′ groups are carbon monoxide, phosphines, especially trimethylphosphine, triethylphosphine, triphenylphosphine and bis (1,2-dimethylphosphino) ethane, R is P _{(OR) 3} is a _{C. 1 to 20} hydrocarbyl, ethers, in particular tetrahydrofuran, amines, especially pyridine, bipyridine, tetramethylethylenediamine (T
MEDA), and triethylamine, a conjugated _{C 4 to 4 0} dienes olefins, and neutral. Complexes containing such neutral diene X 'groups are those in which the metal is in the +2 form oxidation state.

Preferably, the catalyst comprises a coordination complex corresponding to Formula III

[0041]

Embedded image

Wherein R ₁ and R ₂ are independently a group selected from hydrogen, hydrocarbyl, perfluorinated hydrocarbyl, silyl, germyl and mixtures thereof, wherein said group has up to 20 non-hydrogen atoms Including at least one of R ₁ or R ₂
Is not hydrogen, and R ₃ , R ₄ , R ₅ , and R ₆ are independently a group selected from hydrogen, hydrocarbyl, perfluorinated hydrocarbyl, silyl, germyl, and mixtures thereof; Up to non-hydrogen atoms, M is titanium, zirconium or hafnium, and Z is boron or 14
A divalent moiety comprising a member of the group III and also containing nitrogen, phosphorus, sulfur or oxygen, wherein said moiety contains up to 60 non-hydrogen atoms, p is 0, 1 or 2; Or 1, provided that when p is 2, q is 0, M is in a +4 form oxidation state, and X is halide, hydrocarbyl, hydrocarbyloxy, di (hydrocarbyl) amide, di (hydrocarbyl) phosphide, hydrocarbyl sulfide And silyl groups, and anionic ligands thereof selected from halo, di (hydrocarbyl) amino, hydrocarbyloxy, and di (hydrocarbyl) phosphino substituted derivatives, wherein X has up to 20 non-hydrogen atoms , P is 1, q is 0, M is a +3 type oxidation state, X is allyl, 2- (N, N-dimethylamino-methyl) Phenyl, and 2-(N, N-dimethyl) - a stable hung ionic ligand group selected from the group consisting of aminobenzyl, or M is +
X is a four-form oxidation state, X is a divalent derivative of a conjugated diene, M and X together form a metallocyclopentene group, q is 1 when p is 0, and M is a + 2-form oxidation state X 'is a neutral conjugated or non-conjugated diene, optionally substituted with one or more hydrocarbyl groups, said X' having up to 40 carbon atoms and together with M, a π complex To form

[0043] Most preferred coordination complexes, (t-butylamido) - dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane titanium (II) 1,3-pentadiene is referred as geometric isomers Have two isomers, Formulas IVA and IVB.

[0044]

Embedded image

Specific examples of coordination complexes are described in PCT / US97 / 07 already incorporated by reference.
252, page 10, line 3 to page 16, line 36. The coordination complex, (t-butylamido) dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane titanium (II) 2,4-hexadiene, (t-butylamido) - dimethyl (eta ⁵ -2-methyl-s-indacen-1-yl) silanetitanium (IV) dimethyl, (t-butylamido) -dimethyl (η ⁵ -2,3
-Dimethylindenyl) silane titanium (II) 1,4-diphenyl-1,3
-Butadiene, (t-butyl-amido) -dimethyl (η ⁵ -2,3-dimethyl-
(s-indacen-1-yl) silanetitanium (IV) dimethyl and (t-
Butylamido) - dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane titanium (II) is preferably selected from the group consisting of 1,3-pentadiene. Preferred members of this group, (t-butylamido) - dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane - titanium (IV) dimethyl, (t-butylamido) dimethyl (eta ⁵ -2 - methylindenyl) - silanetitanium (II) 2,4-hexadiene, and (t-butylamido) - dimethyl (eta ^5-2-methyl -s- indacene-1-yl) silane titanium (II) 1
, 3-pentadiene. The most preferred coordination complex is (t-butylamido) -dimethyl ([eta] < ⁵ > -2-methyl-s-indacene-1-yl) silanetitanium (II) 1,3-pentadiene.

Other preferred metal complexes include derivatives of transition metals, including lanthanides, but with a +2, +3, or +4 formal oxidation state that meets the previously described needs.
Group 4 or lanthanide metals are preferred. Preferred compounds include metal complexes (metallocenes) containing 1 to 3π-linked anionic ligand groups, which can be cyclic or acyclic delocalized π-linked anionic ligand groups. Examples of such π-bonded anionic ligand groups include conjugated or non-conjugated, cyclic or acyclic dienyl groups, allyl groups, and arene groups. Such other preferred metal complexes correspond to the formula L ₁ MX _m X ′ _n X ″ _{p ′s} or a dimer thereof, wherein:
L is an anion delocalized π-bonded group attached to M, containing up to 50 atoms without counting hydrogen, optionally wherein two L groups are linked together by one or more substituents And thereby forming a crosslinked structure, and optionally one L can be linked to X by one or more L substituents, and M is a formal oxidation of +2, +3 or +4 A metal of Group 4 of the Periodic Table of the Elements, where X is optionally 50
X 'is a divalent substituent of up to 20 non-hydrogen atoms, forms a metallocycle with M together with L, X' is a neutral Lewis base optionally having up to 20 non-hydrogen atoms, X ''Is a monovalent anion moiety having up to 40 non-hydrogen atoms per occurrence;
Optionally, the two X '' groups are linked together to form a divalent dianion moiety with both valencies attached to M, or π-attached to M (where M is a +2 oxidation It is possible to form a neutral conjugated or non-conjugated diene), or optionally, one or more X ″ and one or more X ′ groups linked together thereby Both can be covalently linked to M to form a moiety coordinated to them by Lewis base function, 1 is 1 or 2, m is 0 or 1, and n is 0 to 3. A number, p is an integer from 0 to 3, and l +
The sum of m + p equals M formal oxidation states. Variants of such a complex have X ″ containing up to 20 non-hydrogen atoms at each occurrence, and the two X ″ groups together have m =
Form a neutral _C5-30 conjugated diene where 1 and p are 1 or 2.

Preferred divalent X substituents contain up to 30 atoms without counting hydrogen and are directly attached to a delocalized π-bonded group, either oxygen, sulfur, boron or one of group 14 of the periodic table. A group comprising at least one member of the group and a different atom selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur covalently bonded to M.

[0048] Such other preferred conjugates include those containing one or two L groups. The latter conjugates include those containing a bridging group linking two L groups.
Preferred bridging groups are those corresponding to the formula (ER ^* ₂ ) _x , wherein E is silicon or carbon and R ^* is independently at each occurrence hydrogen or silyl, hydrocarbyl,
A group selected from hydrocarbyloxy and combinations thereof, wherein said R ^* has up to 30 carbon or silicon atoms and x is 1 to 8. Preferably, R ^* is independently at each occurrence methyl, benzyl, tert-butyl or phenyl.

Illustrative of said bis (L) comprising complexes are compounds corresponding to formulas V and VI:

[0050]

Embedded image

Wherein M is titanium, zirconium having a positive oxidation state of +2 or +4
Or hafnium and R³Is independently hydrogen, hydrocarbyl, di
Hydrocarbylamino, hydrocarbyleneamino, silyl, germyl, cyano,
Selected from the group consisting of halo and combinations thereof,³Puts hydrogen in the number
Having up to 20 atoms, or adjacent R³Groups together form a divalent derivative
Thereby forming a fused ring system, with each occurrence of X '' being independent of the number of hydrogens
An anionic ligand group of up to 40 atoms, or two X '' groups together
Form a divalent anionic ligand group of up to 40 atoms without counting hydrogen
Or a conjugated diene having from 4 to 30 atoms which together do not count hydrogen.
And forms a π complex with M, where M is in the +2 form oxidation state and R ^* , E and x are as defined above.

The above-described metal complex is particularly suitable for producing a polymer having a stereoregular molecular structure. With such ability, the conjugate has C ₂ symmetry or is chiral,
It preferably has a three-dimensionally rigid structure. An example of the first class is a compound having a different delocalized pi-bond system, such as one cyclopentadienyl group and one fluorenyl group. Similar systems based on Ti (IV) or Zr (IV)
Ewen, et al. J. Am. Chem. Soc. 110, 6255-6
256 (1980) for the preparation of syndiotactic olefin polymers. Examples of chiral structures include bis-indenyl conjugates. Similar systems based on Ti (IV) or Zr (IV) are described by Wild et al.
al. J. Organomet. Chem, 232, 233-47, (19
82) for the production of isotactic olefin polymers.

Examples of bridging ligands containing two π-bonded groups are (dimethylsilyl-bis-cyclopentadienyl), (dimethylsilyl-bis-methylcyclopentadienyl)
, (Dimethylsilyl-bis-ethylcyclopentadienyl, (dimethylsilyl-
(Bis-t-butylcyclopentadienyl), (dimethylsilyl-bis-tetramethylcyclopentadienyl), (dimethylsilyl-bis-indenyl), (dimethylsilyl-bis-tetrahydroindenyl), (dimethylsilyl-bis -Fluorenyl), (dimethylsilyl-bis-tetrahydrofluorenyl), (dimethylsilyl-bis-2-methyl-4-phenylindenyl), (dimethylsilyl-
(Bis-2-methylindenyl), (dimethylsilyl-cyclopentadienyl-fluorenyl), (1,1,2,2-tetramethyl-1,2-disilyl-bis-cyclopentadienyl), (1, 2-bis (cyclopentadienyl) ethane, and (isopropylidene-cyclopentadienyl-fluorenyl).

Preferred X ″ groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl groups, wherein the two X ″ groups together form a divalent derivative of a conjugated diene. Or together form a neutral, π-bonded conjugated diene.

Preferred geometrically constrained metal composites are also described in US-A-5, already incorporated by reference.
No. 4,709,93, US Pat. No. 5,559,928 and US Pat. No. 5,624,878, which correspond to the Group 4 metal coordination complexes corresponding to formula VII below. See, for example, U.S. Pat.

[0056]

Embedded image

Wherein M is titanium, zirconium, which has a positive oxidation state of +2 or +4
And R³Is independently at each occurrence hydrogen, hydrocarbyl, silyl, germyl,
R is selected from the group consisting of cyano, halo, and combinations thereof;³Is hydrogen
Having up to 20 atoms uncounted or adjacent R³Groups are divalent together
Form (ie, hydrocarbadiyl, siladiyl, or germadiyl group)
And thereby forming a fused ring system, wherein each X ″ is halo, hydrocarbyl, hydride
Locarbyloxy or silyl groups, up to 20 groups without counting hydrogen.
Or two X ″ s together form C_5-30Form a conjugated diene,
Y is -O-, -S-, -NR^*-, -PR^*And Z is SiR^* ₂, CR^* ₂ , SiR^* ₂SiR^* ₂, CR^* ₂CR^* ₂, CR^*= CR^*, CR^* ₂Si
R^* ₂Or GeR^* ₂And R^*Is as defined above.

The above-mentioned delocalized π-bonding group, metal complexes containing the same and catalyst compositions based on them are disclosed in the following publications, US Pat. Nos. 5,703,187, 5064802, 5321106,
5374696, 5470993, 5624878, 5556928, 5486
632, 55541349, 5495036, 5527929, 5661664,
Fully disclosed by WO 97/15583, WO 97/35864, WO 98/06727, and WO 98/27103, the teachings of which or corresponding, equivalent US patent applications are incorporated herein by reference.

Examples of Group 4 metal composites are described in US Pat.
It is found on line 9. Some of these complexes include: (Te
rt-butylamide)-(tetramethyl-η⁵-Cyclopentadienyl) dimethyi
Rusilane titanium dichloride, (tert-butylamide) (tetramethyl-
η⁵-Cyclopentadienyl) dimethylsilanetitanium dimethyl, tert-
Butylamide) (tetramethyl-η⁵-Cyclopentadienyl) -1,2-ethane
N-diyltitanium dimethyl, (tert-butylamide) (hexamethyl-η ⁵ -Indenyl) dimethylsilanetitanium dimethyl, (tert-butylamido)
C) (tetramethyl-η⁵-Cyclopentadienyl) dimethylsilanetitanium
(III) 2- (dimethylamino) benzyl, (tert-butylamide) (
Tramethyl-η⁵-Cyclopentadienyl) -dimethylsilanetitanium (II
I) Allyl, (tert-butylamide) (tetramethyl-η⁵-Cyclopentane
Dienyl) -dimethyl-silanetitanium (II) 1,4-diphenyl-1,3
-Butadiene, (tert-butylamido) (2-methylindenyl) dimethyl
-Silane titanium (II) 1,4-diphenyl-1,3-butadiene, (te
rt-butylamido) (2-methylindenyl) dimethyl-silanetitanium (
IV) 1,3-butanediene, (tert-butylamide) (2,3-dimethyl
Indenyl) dimethylsilanetitanium (II) 1,4-diphenyl-1,3-
Butadiene, (tert-butylamide) (2,3-dimethylindenyl) dimethyl
Tylsilanetitanium (IV) 1,3-butadiene, (tert-butylamide
) (2,3-Dimethylindenyl) -dimethylsilanetitanium (II) 1,3
-Pentadiene, (tert-butylamide) (2-methylindenyl) dimethyi
Silane-titanium (II) 1,3-pentadiene, (tert-butylamide
) (2-dimethylindenyl) dimethylsilanetitanium (IV) dimethyl, (
tert-butylamide) (2-methyl-4-phenylindenyl) -dimethyl
Silantitanium (II) 1,4-diphenyl-1,3-butadiene, (ter
t-butylamide) (2-methyl-4-phenylindenyl) -dimethylsilane
Titanium (II) 1,3-pentadiene, (tert-butylamide) (tetra
Lamethyl-η⁵-Cyclopentadienyl) -dimethylsilanetitanium (IV)
1,3-butadiene, (tert-butylamide) (tetramethyl-η⁵-Shiku
(Lopentadienyl) -dimethylsilanetitanium (II) 1,4-dibenzyl-
1,3-butadiene, (tert-butylamide)-(tetramethyl-η⁵−
Clopentadienyl) dimethyl-silanetitanium (II) 2,4-hexadie
, (Tert-butylamide) (tetramethyl-η⁵-Cyclopentadienyl
) -Dimethylsilanetitanium (II) 3-methyl-1,3-pentadiene,
tert-butylamide) (2,4-dimethyl-1,3-pentadiene-2-i
B) dimethylsilanetitanium dimethyl, (tert-butylamide) (1,1
-Dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydride
Ronaphthalen-4-yl) dimethyl-silanetitaniumdimethyl, (tert-
Butylamide) (1,1,2,3-tetramethyl-2,3,4,9,10-η-
1,4,5,6,7,8-hexahydronaphthalen-4-yl) dimethylsilane
Titanium dimethyl, (tert-butylamide) (tetramethyl-cyclopen
Tadienyl) -dimethylsilanetitanium 1,3-pentadiene, (tert-
Butylamido) (3- (N-pyrrolidinyl) inden-1-yl) dimethylsila
1,3-pentadiene, (tert-butylamide) (2-methyl
-S-Indacene-1-yl) dimethylsilanetitanium 1,3-pentadiene
, (Tert-Butylamide) (2-methyl-s-indacene-1-yl) dimene
Tylsilanetitanium 1,4-diphenyl-1,3-butadiene, and (te
rt-butylamido) (3,4-cyclopenta (l) phenanthren-2-yl
) Dimethylsilane-titanium 1,4-diphenyl-1,3-butadiene. 4th family
The metal complex is (tert-butylamide)-(tetramethyl-η⁵-Cyclopen
Tadienyl) -dimethylsilane titanium η⁴-3-methyl-1,3-pentadi
En and C₅Me₄SiMe₂NtBu) Ti (η⁴-1,3-pentadiene
) Is preferred.

Complexes containing bis (L), including crosslinked complexes suitable for use in the present invention, include biscyclopentadienyl zirconium dimethyl, biscyclopentadienyl-titanium diethyl, biscyclopentadienyl titanium Diisopropyl, biscyclopentadienyl titanium-diphenyl, biscyclopentadienyl zirconium dibenzyl, biscyclopentadienyl titanium-2,4-pentadienyl, biscyclopentadienyl-titanium methyl methoxide, biscyclopentadienyl titanium Methyl chloride, bispentamethylcyclopentadienyltitanium dimethyl, bisindenyltitanium-dimethyl, indenylfluorenyltitaniumdimethyl, bisindenyltitaniummethyl (2- (dimethylamino ) -Benzyl), bisindenyltitanium methyltrimethylsilyl,
Bistetrahydroindenyl-titanium methyltrimethylsilyl, bispentamethylcyclopentadienyltitanium diisopropyl, bispentamethylcyclopentadienyltitanium dibenzyl, bispentamethylcyclopentadienyl-titanium methylmethoxide, bispentamethylcyclopentadienyl Titanium methyl chloride, (dimethylsilyl-bis-cyclopentadienyl) zirconium dimethyl, (dimethylsilyl-bis-pentamethyl-cyclopentadienyl) titanium-2,4-pentadienyl, (dimethylsilyl-bis-t-butylcyclopentane) (Dienyl) -zirconium dichloride, (methylene-bis-pentamethylcyclopentadienyl) titanium (III) 2- (dimethylamino) benzyl, (dimethyl Rushiriru - bis - indenyl) zirconium dichloride, (
Dimethylsilyl-bis-2-methylindenyl) zirconium dimethyl, (dimethylsilyl-bis-2-methyl-4-phenylindenyl) -zirconium dimethyl, (dimethylsilyl-bis-2-methylindenyl) -zirconium-1 ,
4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-2-methyl-
4-phenylidenyl) zirconium (II) 1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-tetrahydroindenyl) zirconium (
II) 1,4-diphenyl-1,3-butadiene, (dimethylsilyl-bis-fluorenyl) zirconium dichloride, (dimethylsilyl-bis-tetrahydrofluorenyl) -zirconium-di (trimethylsilyl), (isopropylidene) (cyclo Pentadienyl) (fluorenyl) -zirconium dibenzyl, and (dimethylsilylpentamethylcyclopentadienylfluorenyl) -zirconium dimethyl.

[0061] The metal complexes described above can be prepared by using well-known synthetic techniques. Optionally, a reducing agent can be used to produce a low oxidation state complex. Such a method is described in WO95-, the teachings of which are incorporated herein by reference.
U.S. Patent No. 8/241523, published May0052, May 1, 1994.
3rd, and WO98 / 27103 and PCT / US97 / 07252 (
Already incorporated by reference). The synthesis is carried out in a suitable unhindered solvent,
It is carried out at a temperature between -100 and 300C, preferably between -78 and 100C, most preferably between 0 and 50C. As used herein, the term "reducing agent" refers to a metal or compound that reduces metal M from a high oxidation state to a low oxidation state under reducing conditions. Illustrative examples of suitable metal reducing agents are alkali metals, alkaline earth metals, alloys of alkali metals or alkaline earth metals such as aluminum and zinc, sodium / mercury amalgam and sodium / potassium alloys. Examples of suitable reducing agent compounds are: Group 1 or 2 metal hydrocarbyl compounds having 1 to 20 carbons in each hydrocarbyl group, such as sodium, potassium graphite, alkyllithium, alkadienyllithium or potassium naphthalenide and Grignard It is a reagent. Most preferred reducing agents are alkali or alkaline earth metals, especially lithium and magnesium metals.

[0062] Reaction solutions suitable for complex formation include aliphatic and aromatic hydrocarbons, ethers,
And branched ethers such as cyclic ethers, especially isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, and cyclic and alicyclic rings such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. Includes aromatic and hydrocarbyl-substituted aromatic compounds such as formula hydrocarbons, benzene, toluene, and xylene, C _1-4 dialkyl ethers, C _1-4 dialkyl ether derivatives of (poly) alkylene glycols, and tetrahydrofuran. The above mixtures are also suitable.

A catalyst complex, a mixture of coordination complexes, or both can be used in the method embodiments of the present invention. For example, WO98 / 27103 and PCT / US9
The coordination complex described in 7/07252 can be used in combination with a catalyst complex as described, for example, in US Pat. No. 5,470,993. Similarly, W
Combinations of two or more coordination complexes disclosed in O98 / 27103 and PCT / US97 / 07252, or 2 disclosed in US Pat. No. 5,470,993.
More than one catalyst complex also produces acceptable results.

The above-described catalyst composite is illustrative and not limiting. A catalyst that promotes vinyl end group termination upon polymerization conditions and subsequent reinsertion into the polymer chain is considered to be sufficient as long as the resulting polymer has a PRR of at least 4.

The conjugate, whether a catalyst conjugate or a coordination conjugate, or both, is made catalytically active by combining with an activating catalyst or by using an activating method. Activating catalysts suitable for use herein include poly or oligoalumoxanes, especially methylalumoxane, triisobutylaluminum-modified methylalumoxane, or isobutylalumoxane, _C1-30 hydrocarbyl-substituted Group 13 compounds, and the like. Neutral Lewis acids, especially tri (hydrocarbyl) aluminum or tri (hydrocarbyl) boron compounds and their halogenated derivatives (including perhalogenated) having from 1 to 10 carbon atoms in each hydrocarbyl or halogenated hydrocarbyl group, In particular, it includes perfluorinated tri (aryl) borane compounds, and most particularly tris (pentafluorophenyl) borane (hereinafter “FAB”).

Alternatively, the complex may be converted to a non-polymerized compatible non-coordinating ion-forming compound (including the use of such compounds under oxidizing conditions), particularly ammonium salts, phosphonium salts, oxoniums of compatible non-coordinating anions. Catalytic activation is achieved by combining with a salt, a carbonium salt, a silylium salt or a sulfonium salt or a ferrocenium salt of a compatible non-coordinating anion, and a combination of the activating cocatalysts and techniques described above. The activating cocatalysts and activating techniques have been previously described in the following reference, EP-A-2.
77003, US-A-5153157, US-A-5064802, EP-A
-468651 (equivalent to US patent application Ser. No. 07 / 47,718), EP-A-5
20732 (equivalent to US patent application Ser. No. 07 / 876,268), and EP-A-5
No. 20732 (U.S. patent application Ser. No. 07 / 884,966, filed May 1, 1992) teaches about different metal composites, the teachings of which are incorporated herein by reference.

Combinations with neutral Lewis acids, especially trialkylaluminum compounds having 1 to 4 carbon atoms in each alkyl group and tri (hydrocarbyl) boron halides having 1 to 20 carbon atoms in each hydrocarbyl group Combinations of compounds, especially FAB, and also such combinations of neutral Lewis acid mixtures with poly or oligoalumoxanes, combinations of neutral neutral Lewis acids alone, especially FAB with poly or oligoalumoxane are particularly desirable activities. It is a chemical cocatalyst. Group 4 metal complex: FAB:
The preferred molar ratio of alumoxane is from 1: 1: 1 to 1: 5: 20, 1: 1: 1
. 5 to 1: 5: 10 is more preferred. The use of a low concentration of alumoxane in the process of the present invention allows for the production of EAODM polymers having high catalytic effects with little use of expensive alumoxane cocatalysts. In addition, polymers are thus obtained which have a distinctly lower concentration of aluminum residues.

Further suitable ion-forming, activating cocatalysts include compounds which are salts of silylium ions and non-coordinating, compatible anions of the formula R ₃ Si (X ′) _q ⁺ A ⁻ , Wherein R is C _1-10 hydrocarbyl, and X ′, q and A ⁻ are as previously defined.

Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluoro-phenylborate, triethylsilylium tetrakispentafluorophenylborate and their ether-substituted additives. Silylium salts are already generally described in J.I. Chem. Soc. Chem. Comm. , 1993, 383
384, and Lambert, J. et al. B. Et al. , Organom
et allics, 1994, 13, 2430-2443. Use of the silylium salt as an activating catalyst for an additional polymerization catalyst is described in 199
The equivalents are disclosed in U.S. Patent Application No. 304314, published on March 21, 1994, WO 96/08519, filed September 12, 1994, the teachings of which are incorporated herein by reference.

Certain complexes of oximes of alcohols, mercaptans, silanols, and FAB are also effective catalyst activators and can be used in accordance with the present invention. Such catalysts are disclosed in US Pat. No. 5,296,433, the teachings of which are incorporated herein by reference.

The technique of bulk electrolysis involves the electrochemical oxidation of a metal complex under electrolysis conditions in the presence of a supporting electrolyte containing a non-coordinating inert anion. This technique is more fully described from column 15, line 47 to column 16, line 48 of US-A-5624878, already incorporated.

The catalyst / cocatalyst molar ratio used is preferably in the range from 1: 10000 to 100: 1, more preferably from 1: 5000 to 10: 1, most preferably from 1: 1000 to 1: 1. Alumoxane is used in large amounts when used alone as the activating cocatalyst, generally at least 100 times the amount of metal complex (calculated in moles of aluminum (Al)) on a molar basis. FAB, when used as an activating cocatalyst, has a molar ratio to the metal complex of from 0.5: 1 to 10: 1, more preferably from 1: 1 to 6: 1, and most preferably from 1: 1 to 5: 1. : 1 is used. The remaining activating cocatalyst is generally used in approximately equimolar amounts with the metal complex.

Generally, the polymerization is carried out by Ziegler-Natta or Kaminsky-Si.
Conditions well known in the art for nn-type polymerization reactions, i.
It is possible to work at 250 ° C., preferably 30 to 200 ° C., at a pressure from atmospheric to 10,000 atm. For example, soluble bis (cyclopentadienyl) zirconium dimethyl- for solution polymerization of EP and EAODM elastomers
Kaminsky, J., who reports the use of an alumoxane catalyst system. Poly. S
ci. Vol. 23, pp. 2151-64 (1985). US
P5229478 discloses a slurry polymerization method using bis (cyclopentadienyl) zirconium based on a similar catalyst system.

[0074] Suspensions, solutions, slurries, gas phase, solid phase powder polymerization or other process conditions can be used if desired. Supports, especially silica, alumina,
Or polymer (especially poly (tetrafluoroethylene) or polyolefin)
And it is desirable to use the catalyst when it is used in a gas phase polymerization method. The support has a catalyst (metal-based): support weight ratio of 1: 1.
Preferably, it is used in an amount providing from: 1,000,000 to 1:10, more preferably from 1: 50,000 to 1:20, most preferably from 1: 10000 to 1:30. In most polymerization reactions, the catalyst the molar ratio of polymerizable compound ^used was ^{10 -12:} 1 to ¹⁰ -1: 1, more preferably from ^{10 -9:} 1 to ^{10 -} 5: 1. The method used to prepare the EAODM interpolymer of the present invention is a solution method or a slurry method, both of which are already known in the art.

The inert liquid is a solvent suitable for the polymerization. Examples include straight and branched chain hydrocarbons such as isobutane, butane, pentane, hexane, heptane, octane, and mixtures thereof, cyclohexane, cycloheptane, methylcyclohexane,
Cyclic and alicyclic hydrocarbons such as methylcycloheptane, and mixtures thereof,
Perfluorinated hydrocarbons such as perfluorinated C _4-10 alkanes, benzene, toluene,
Xylene and aromatic and alkyl-substituted aromatic compounds such as ethylbenzene are included. Suitable solvents also include butadiene, cyclopentene, 1-hexene,
1-hexane, 4-vinylcyclohexene, vinylcyclohexane, 3-methyl-1-pentene, 4-methyl-1-pentene, 1,4-hexadiene, 1-octene, 1-decene, styrene, divinylbenzene, allylbenzene, And liquid olefins that can act as monomers or comonomers, including vinyltoluene (including single or mixed isomers). If desired
Normal gaseous olefins can be converted to liquids by applying the pressures used herein.

The catalyst is combined with at least one additional homogeneous or heterogeneous polymerization catalyst in separate reactors connected in series or parallel to prepare a polymer blend having the desired properties. It can be used in combination. Examples of such methods are described in WO 94/00500, equivalent to US patent application Ser. No. 07 / 904,770,
And U.S. patent application Ser. No. 08/10958, filed Jan. 29, 1993, the teachings of which are incorporated herein by reference.

In a method according to one embodiment of the present invention, the catalyst, catalyst complex and
Interpolymers of Other Embodiments of the Invention by Using a Coordination Complex
Is easily prepared. The resulting EAO (D) M interpolymer is NBR or
Shows a PRR of at least 4 without incorporating other conventional LCB monomers. this
The interpolymer has a linear polymer backbone and does not contain LCB.
Improved polymer processability (can include high throughput) for mer
Melt strength, high green strength, reduced pigment odor, resistance to melt breakage, and
Shows the extensibility of the filler.

The catalyst used in the process of the present invention is particularly advantageous for producing an interpolymer having a PRR of at least 4. The use of catalysts in continuous polymerization processes, especially in continuous solution polymerization processes, allows for high reaction temperatures that favor the formation of vinyl terminated polymer chains that can be incorporated into growing polymers, thereby lengthening long chain branching. Get. It is believed that the unique combination of high reaction temperature, high ethylene conversion, and substantially no or very low concentrations of molecular hydrogen produces the desired interpolymer of the first aspect of the present invention. As used herein, "very low concentration"
Means a concentration greater than 0, but less than or equal to 0.1 mole percent, based on the sum of the fresh ethylene feed content and the fresh hydrogen feed content.

In general terms, EAO under conditions where the reactivity of the diene monomer component is increased
It is desirable to produce a DM elastomer. The reason was clarified above
The '487 patent describes in the following way that progress has been achieved in such literature.
Nevertheless, it remains unchanged. Manufacturing costs and therefore EAODM applications
A major factor affecting is the cost of the diene monomer. This diene is C ₂ Or C₃It is a more expensive monomer material. Furthermore, already known metallocenes
The reactivity of the diene monomer with the catalyst is C₂And C₃Lower than. Therefore,
Diene removal required to produce EAODM with acceptable fast cure rates
To achieve a degree of incorporation, expressed as a percentage of the total concentration of monomers present.
Compared to the percentage of diene that is desired to be incorporated into the final EAODM product
It was necessary to use a substantially excessive diene monomer concentration. Non-reactive di
Substantial amounts of ene monomers must be recovered from the polymerization reactor recycle effluent.
Therefore, the manufacturing cost is further increased.

Further, in addition to the cost of EAODM production, olefin polymerization catalysts are generally
There is the fact that the catalyst often reduces the rate or activity that causes the polymerization of the ethylene and polyethylene monomers being processed, especially when exposed to the high concentrations of diene monomer required to provide the required concentration of diene incorporation into the final EAODM. Correspondingly, lower processing power and longer reaction times were required compared to the production of ethylene-propylene copolymer elastomers or other α-olefin copolymer elastomers.

The EAO (D) M polymers of the present invention also use gas phase polymerization, reactor cooling, generally to prepare EAO (D) M polymers, as described above, with recycled gas, inert It is produced by liquids or other well-known methods which occur by evaporative cooling of volatiles such as monomers or any dienes. Suitable inert _{liquid, C. 3 to 8,} preferably _{C 4 to 6,} a saturated hydrocarbon monomers. Volatiles or volatiles are distilled off in a hot fluidized bed to form a gas that mixes with the flowing gas. Methods of this kind are described, for example, in EP 89691, US-A-4543399, WO 94 /
No. 25495, WO 94/28032, and US Pat. No. 5,352,749, the teachings of which are incorporated herein by reference. Other relevant teachings are also incorporated by reference, but US-A-4588790, US-A-4543399.
U.S. Pat. No. 5,352,749, U.S. Pat. No. 5,436,304, U.S. Pat.
922, US-A-5462999, US-A-5461123, US-A-5
453471, US-A-5032562, US-A-5028670, US-
A-5473028, US-A-5106804, US-A-5541270,
EP-A-657773, EP-A-692500 and PCT application WO94
/ 29032, WO94 / 25497, WO94 / 25495, WO94 / 28
032, WO95 / 13305, WO94 / 26793 and WO95 / 079
42.

The polymerization reaction occurring in the fluidized bed is catalyzed by continuous or semi-continuous addition of the catalyst. Such a catalyst can be supported on an inorganic or organic support material.

A gas phase process suitable for practicing the present invention is a large-scale gas phase reactor reaction zone by continuously feeding reactants to the reaction zone of the reactor and removing products from the reaction zone of the reaction vessel. A continuous method that produces a stable environment is preferred.

[0084] In contrast, solution polymerization conditions use a solvent for each component of the reaction. Preferred solvents include mineral oils and various hydrocarbons liquid at the reaction temperature. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane, as well as kerosene and Exxon Chemical
s Inc. Alkane mixtures such as Isopar E ™, cycloalkanes such as cyclopentane and cyclohexane, and aromatics such as benzene, toluene, xylene, ethylbenzene and diethylbenzene.

At any time, each component as well as the recovered catalyst component should be protected from oxygen and moisture. Therefore, the catalyst components and catalyst should be prepared and recovered in an oxygen and moisture free atmosphere and are preferred. Thus, the reaction is preferably carried out in the presence of a dry, for example inert gas such as nitrogen.

Ethylene is added to the reaction vessel in an amount sufficient to maintain a differential pressure above the combined vapor pressure of the α-olefin and diene monomer. C ₂ content of the polymer is determined by the ratio of C ₂ differential pressure to the total reactor pressure. Generally, the polymerization is carried out at a C ₂ differential pressure of 10 to 1500 pounds per square inch (psi) (70 to 1050
0 kPa), most preferably 40 to 800 psi (280 to 5600 kPa).
). The polymerization temperature is 70 to 225 ° C, preferably 80 to 170 ° C,
Most preferably above 80 and up to 140 ° C.

The polymerization reaction is at least 60 wt% based on the amount of ethylene fed to the reactor.
It is desirable to carry out the reaction under conditions sufficient to achieve ethylene conversion. This ethylene conversion is preferably above 65 wt%, more preferably above 70 wt%. The polymer concentration in the reactor in the steady state condition solution method is desirably 5 to 25 wt%, preferably 8 to 25 wt%, and most preferably 10 to 20 wt%. Using a polymer concentration of the solution method of greater than 25 wt%, it is possible that the resulting polymer solution also has a solution viscosity that is advantageous for processing. Methods other than the solution method, such as the slurry method or the gas phase method, are different, but have a rapidly measured polymer concentration limit.

The polymerization can be carried out using one or more reactors, either in a batch or continuous polymerization process. The polymerization is preferably carried out by a continuous process such that the catalyst, ethylene, α-olefin, diene and any solvent are continuously supplied to the reaction zone and the polymer product is continuously removed therefrom.

Without limiting the scope of the present invention, one means for performing such a polymerization process is a stirred tank reactor that continuously introduces an α-olefin monomer with a solvent, a diene monomer and a C ₂ monomer. Use The reaction vessel comprises a substantially C _2, C ₃ and diene (also known as "polyene") liquid phase comprising the monomer with a solvent or additional diluent. If desired, conventional LCBs containing dienes such as NBD, 1,7-octadiene or 1,9-decadiene can also be added in small amounts, as long as the desired polymer properties are not adversely affected. The catalyst and cocatalyst are continuously introduced into the reactor liquid phase. Reactor temperature and pressure can be controlled by adjusting the solvent / monomer ratio, catalyst addition rate, and using cooling or heating coils, jackets, or both. The catalyst addition rate controls the polymerization rate. By manipulating the respective feed rates of ethylene, α-olefin and diene to the reaction vessel, control of the ethylene content of the polymer product is achieved. Polymer product molecular weight is controlled by control of temperature, monomer concentration or other polymerization variables such as introduction of a stream of hydrogen into the reactor. The reactor effluent contacts a catalytic decomposer, such as water. The polymer solution is optionally heated to exhaust gaseous ethylene and polyethylene and residual diene and residual solvents or diluents under reduced pressure and, if necessary, further devolatilized with a devolatilizing extruder or other device. To recover the polymer product. In a continuous process, the average residence time of the catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, preferably from 10 minutes to 6 hours.
Time.

In a preferred mode of operation, the polymerization involves two series or parallel connected reactors.
In a continuous solution polymerization system. In one reactor, a relatively high molecular weight product (M _W 50,000 to 1,000,000, more preferably 100,000 to 50,000
0) is formed without hydrogen, while in the second reactor relatively low molecular weight products (
M_W20,000 to 300,000). The presence of hydrogen in the second reactor
Is optional. Alternatively, the same molecular weight product is placed in each of the two reactors.
And can be generated. The final product is a homogeneous blend of the two polymer products
With the blend of the two reactor effluents combined prior to volatilization to obtain
is there. The production of products with improved properties by such a dual reactor method is conceivable.
You. In a preferred embodiment, the reactors are connected in series and the discharge from the first reactor
The product is charged to a second reactor and fresh monomer, solvent and hydrogen are transferred to the second reactor.
Is added. The reactor conditions were the first reaction to the polymer produced in the second reactor.
The weight ratio of the polymer produced in the vessel is adjusted to be from 20:80 to 80:20.
You. However, if desired, a wider range of weight ratios can be used.
. If desired, it is also possible to use different catalyst systems for each reactor.
. For example, one reactor may use the metallocene-based catalyst system outlined above.
Depending on the process conditions used, in the second reactor a conventional Ziegler-Natta or
Are based on other types of metallocenes that can use the outlined method conditions
Catalyst system. Further, the temperature of the second reactor is controlled to reduce the M_WProduce product
You. This system allows E to have a wide MV range and excellent strength and workability.
A beneficial production of AODM products is conceivable. The preferred mode of operation is to use two reactors
Although used, more than two reactors can also be used.

EXAMPLES The following examples are illustrative and do not limit the invention, whether explicitly or not. All parts and percentages are by weight unless otherwise indicated.

Several standard tests are used to evaluate the physical properties of EAODM. This test includes MV, Fourier Transform Infrared Analysis (FTIR) (ASTM D3900)
And density (ASTM D-792). Other specific properties include the rheological ratio measured as follows and the PRR measured as described above.
Is included.

RR (V _0.1 / V ₁₀₀ ) is Rheometric Scientific
c, Inc. ARES (Advanced Rheometric Expand)
Measurements are made by testing the samples using a melting rheology technique on a Sion System dynamic mechanical spectrometer (DMS). The samples are tested at 190 ° C. using a 25 mm (mm) radius parallel stationary plate with 2 mm spacing in dynamic frequency mode. Five data points taken at each frequency of 10 are analyzed at a strain rate of 8% and a vibration rate increasing from 0.1 to 100 rad / sec. Each sample (pellet or bail) was subjected to 20,000 psi (137.
It is compression molded to a size of 3 inches (1.18 centimeters (cm)) and 1/8 inch (0.0049 cm) thick at a pressure of 9 megapascals (MPa). The plaque is quenched and cooled to room temperature (over 1 minute). 2 from the center of the large plaque
Cut out 5 mm plaque. These 25 mm diameter sections are then inserted into the ARES at 190 ° C. and allowed to equilibrate for 5 minutes before starting the test. The sample is kept under a nitrogen atmosphere during the analysis to minimize oxidative degradation. Data processing and operations are described in ARES2 / A5: RSI Orchestrator Window.
Implemented by s®95 based software package. RR measures the ratio of viscosity to shear rate curve.

The interpolymer MV (ML _{1 + 4 at} 125 ° C.) is measured according to American Society for Testing and Materials test D1646-94 (ASTM D1646-94). PRR is calculated from MV and RR according to the formulas listed above.

[0095] Polymer MWD is measured by gel permeation chromatography (GPC) using a Millipore / Water 150-C ALC / GPC chromatograph. 0.10 milligrams (mg) of the interpolymer sample was added to 1,2,4-trichlorobenzene 50
. Add to 0 milliliters (ml) and heat at 160 ° C. for 2 hours. After this, 5m
An aliquot is dispensed into a one-drum (0.37 centiliter) automatic sample vial and placed in the instrument archive by a rotating rack with 16 storage locations. After equilibration at 130 ° C. for 90 minutes in the chromatograph, a 100 microliter sample portion was
er Labs PLgel® 10 micrometer Mixed-B
The 900 × 7.5 millimeter GPC column is injected at a flow rate of 1 ml per minute under conditions sufficient to achieve an elution time of 60 minutes. The concentration response of the eluate is measured using a Millipore / Water Differential Refraction Index Detector. Data collection, processing and manipulation are performed using Calibration based on NBS tracking polystyrene standards using TriSec v2.7 software.

[0096] Catalytic efficiency (Cat. Eff.) Is expressed as millilbs of polymer per pound of Group 4 metal in the catalyst (MM # / #). In the batch method, the weight of the polymer product is determined and determined by dividing by the amount of Group IV metal added to the reactor. In the continuous method, the polymer product weight is determined by measuring ethylene or outlet conversion.

Examples 1-3 Three sample ethylene / propylene / ENB interpolymer compositions all represent the present invention and were devised for continuous addition of reactants and continuous removal of polymer solution. Prepared using a single loop reactor. After removing the polymer solution from the reactor, devolatilization and polymer recovery are performed. Catalysts of Examples 1 and 2, respectively cocatalyst and scavenger, (t-butylamido) - dimethyl (eta ^5-2-methyl -
(s-indacen-1-yl) silanetitanium (II) 1,3-pentadiene,
FAB and MMAO (triisobutylaluminum-modified methylalumoxane)
It is. The preparation of this catalyst was described in detail (already incorporated by reference) in PCT /
See Example 3 of US 97/07252. This catalyst of Example 3 is (tetramethylcyclo-pentadienyl) dimethyl (t-butylamido) -silanetitanium 1,3-pentadiene. Example 1 uses a reactor temperature of 120 ° C. and 92.3% ethylene conversion to obtain an interpolymer product. In Example 2, an interpolymer product is obtained using a reactor temperature of 126 ° C. and 86.1% ethylene conversion. Neither embodiment uses a gaseous hydrogen (H ₂ ) stream. Examples 1 and 2 are both 473 pounds per square inch (3.26
A pressure of megapascals (MPa) is used. Example 3 has a 10 standard cubic centimeters per minute _{H 2} flow rate (sccm), a pressure 795psig (5.5
MPa) and a reactor temperature of 101 ° C. are used.

The interpolymer is PCT / US97 / 072 (already incorporated by reference).
As a variation of Example 3 only considering the absence of hydrogen in 52, it is produced using the procedure outlined in Example 4. Thus, ethylene and polyethylene are mixed alkane solvents (Isopar-E ™, Exxon Chemical)
als Inc. And ENB are combined into one stream before being introduced into the dilute mixture comprising ENB and ENB to form a combined feed mixture. The combined feed mixture is continuously injected into the reactor. The blend of the catalyst, cocatalyst, and capture compound combine into a single stream and are continuously injected into the reactor.

Table 1A shows the flow rates of solvents, C ₂ , propylene (C ₃ ) and ENB in pounds per hour (pph). Table IA also shows the catalyst (Cat) concentration parts
per million (ppm) and ppm of cocatalyst (Cocat) and ppm of scavenger (Scav) and Cat, Cocat (FAB) and S
Shows the flow rate pph of cav (MMAO). Table IB shows the catalyst efficiency, the ratio of cocat to metal (M) when M is titanium (Ti), the ratio of scavenger: titanium (Scav / Ti) and the polymer properties (MV and EAODM compositions (F
Measured by TIR)), shows RR, PRR, the _{M W} and MWD. Example 1
_{C 2} Conversion of 3, respectively 92.3Wt%, is 86.1wt% and 83 wt%.

The reactor effluent stream is continuously introduced into the separator and the molten polymer is continuously separated from unreacted comonomer, unreacted ethylene, unreacted ENB, and solvent. The molten polymer is converted to solid pellets by the underwater pelletizer.

[0101]

[Table 1]

[0102]

[Table 2]

The data shown in Examples 1 to 3 show several things. First, polymers with acceptable PRR can be produced in the absence of substantially hydrogen (Examples 1 and 2) or in the presence of very small amounts of hydrogen (Example 3). Second, sufficient PRR values are obtained when changing the interpolymer MW. Third, as shown in Examples 1 and 2, the percent ethylene conversion affects the interpolymer PRR at high conversions (Example 1) resulting in high PRR. Conditions that minimize vinyl end group formation (also known as "vinyl termination"), such as low polymerization temperatures (less than 70 ° C.), high hydrogen concentrations (greater than 0.1 mol%), or both, are all It is believed to lead to an interpolymer of less than PRR4.

Example 4 The EPDM interpolymer uses a double reactor arrangement (with the first reactor connected in series with the second reactor) rather than the single reactor of Examples 1-3. To be prepared. Each reactor is devised and arranged in a manner similar to a single reactor except that polymer recovery is after the second reactor. Polymer production in the first reactor follows the procedure used in a single reactor, without polymer recovery, due to different variables. As in Examples 1 and 2, there is no hydrogen flow in the first reactor. The variables are as follows: C ₂ feed rate 22.9pph, _{C 3} feed rate 9.3pph, ENB feed rate 0.08pp
h, reactor temperature 114 ° C., catalyst flow rate 0.57 pph, cocatalyst (cocat or FAB) flow rate 0.72 pph, scavenger (scav or MMAO) flow rate 0.56
pph, FAB / Ti (cocat / Ti) ratio 3.98, Scav / Ti ratio 3.
98 and _{C 2} conversion 92.9%. The catalyst efficiency is 0.295 MM # / #. Reactor pressure is 475 psig (3.28 MPa).

The product of the first reactor enters the second reactor, where gaseous hydrogen (H₂A new one including
Meet the variables of the ream. This variable is as follows: C₂Feed rate 8.2 pph,
C₃Feed rate 3.9 pph, ENB feed rate 0.03 pph, H₂Supply speed 36
4 sccm (0.018 mol% H₂Fresh H being supplied₂Of fresh H in feeding moles of ₂ Mole and fresh C being supplied₂Mol.), Reactor temperature 110
° C, catalyst flow rate 0.41 pph, FAB flow rate 0.51 pph, MMAO flow rate 0.4
8 pph, cocat / Ti ratio 3.77, Scav / Ti ratio 4.94 and C₂ Conversion 82.6%. The reactor pressure is the same as in the first reactor. The catalyst efficiency is 0.315
MM # / #. The obtained polymer had a propylene content of 28.1% and a content of ENB.
0.55%, any percentage based on the resulting polymer weight.
All MV 22.9, all M_W109100, all MWD 2.85, RR42 and
Based on PRR36.3. A sample of the polymer solution in the first reactor was, by analysis,
PRR76 and M_WThe MV 40 estimated from the above is shown.

The reactor split between the first and second reactors is 59:41, meaning that 59% of the interpolymer is formed in the first reactor. As a first condition in the first reactor, 59% of the interpolymer contains LCB.

Example 4 shows several points as in Example 1-3. First, 4
Even when the favorable conditions for PRR are present in only one of the two reactors, the interpolymers of the present invention can be produced in a dual reactor composition. However, those skilled in the art will realize that in order to achieve a product in the second reactor having a PRR of at least 4, it is necessary that the polymer product in the first reactor have a correspondingly high PRR. It has recognized. Second, the extended M due to the duplex reactor composition
WD does not adversely affect the PRR of the interpolymer.

Example 5 and Comparative Example A Example 4 is repeated using the conditions shown in Tables IIA-IID.

[0109]

[Table 3]

[0110]

[Table 4]

[0111]

[Table 5]

[0112]

[Table 6]

The comparison between Example 5 and Comparative Example A shows the effect on the hydrogen concentration change.
As in Comparative Example A, excess hydrogen causes the PRR to be less than 4.

Example 6 and Comparative Example B EAODM Interpolymer 100 pbw, Low Density Polyethylene (LDPE)
8 pbw (melting index 2 dg / min, density 0.92 grams per cubic centimeter, LD-400, Exxon Chemical), treated clay (vinylsilane treated aluminum silicate (calcined) 60 pbw, Translink®)
37, Engelhard), zinc oxide 5 pbw (zinc oxide 8 in EPDM binder)
5%, ZnO-85-SG, Rhein-Chemie), lead stabilizer 5 pbw
(90% lead red in EPDM binder, TRD-90, Rhein-Chemie),
Paraffin wax 5 pbw (melting point 130-135 degrees F (54-57 degrees C) In
International Waxes, Ltd. ), Antioxidant 1 pbw (polymerized 1,2-dihydro-2,2,4-trimethylquinoline, Agerite® resin D, RT Vanderbilt), crosslinking agent 1 pbw (vinyl- Tris- (2-methoxy-ethoxy) silane 40%, PAC-4
73, OSI Specialties) and 3.5 pbw dicumyl peroxide (
Standard wire and cable compositions, including DiCUP®, Hercules, are processed using a Davis-Standard extruder. In Example 6, this polymer is prepared in the same manner as in Example 4 above, except that the MV is 18 instead of 22. In Comparative Example B, the polymer was Dupont Dow Elastomers L.L. L. C. Nordel® 2722, an ethylene / propylene / 1,4-hexadiene / NBD tetrapolymer commercially available from This extruder is equipped with a barrier screw and a mixing tip, and the ratio of length to diameter (
L / D) is a 3.5 inch (8.9 cm) extruder with a 20: 1 ratio. The extruded tube die has an outer diameter of 52.6 millimeters (mm), an inner diameter of 0.375 inches (9.5 mm) and a length of 0.66 inches (16.8 mm). The extruder has a feed zone, three consecutive mixing zones, a die head zone, and a die zone, each section being 190 ° F. (88 ° C.), 190 ° F. (88 ° C.).
), 200 ° F. (93 ° C.), 200 ° F. (93 ° C.), 225 ° F. (107
° C), and 225 ° F (107 ° C). Table III below shows Example 6.
7 shows extruder operating variables and extrusion characteristics for Comparative Example B and Comparative Example B.

[0115]

[Table 7]

The data in Table III shows that the EPDM interpolymers of the present invention without the conventional LCB monomer provide properties comparable to the extrusion properties of conventional tetrapolymers containing the conventional LCB monomer. This data also applies to the EP of the present invention.
DM interpolymers have been shown to be processed at lower pressures than tetrapolymers by extruders of similar throughput rates.

Example 7-Thermoplastic Elastomer Production TPE was 63% PP (AcPro® 9934, Amoco Ch)
electrical), 27% interpolymer prepared as in Example 4, and 1
Micrometric talc (Microtuf® AG101, Speci
alty Minerals) prepared by combining 10%. This interpolymer has MV18, RR29.3 and PRR24.96. This interpolymer is expected to be MWD 2.8 based on other properties. This combination has a speed of 200 revolutions per minute (rpm) and a set temperature of 2
Occurs in a 30 mm Werner Pfleiderer twin screw extruder operating at 20 ° C and produces an extrudate at a temperature of 225 ° C. The resulting extrudate is 100 tonnes (800 kilonewtons) Ar using a molding temperature of 83 ° F. (28 ° C.).
Mold on a burg molding machine to form test plaques. Various data are obtained in the physical property test of the test plaque. The Shore D hardness at 1 and 10 seconds (ASTM D-2240) of the sample is 62.2 and 58.9, respectively. The test plaque has the following tensile properties (ASTMD-638) when tested at a pull rate of 2 inches per minute (5.1 cm). Tensile strength at break 2599 psi (17.9 MPa), ultimate elongation 44%, tensile strength 3 at the time of formation
064 psi (21.1 MPa) and 6% elongation during formation. Weld line tensile properties (ASTM D-638, 2 inches / 5.1 cm per minute pulling speed)
Has a tensile strength at break of 1877 psi (12.9 MPa), an ultimate elongation of 2%, a tensile strength at the time of formation of 1877 psi (12.9 MPa), and an elongation at the time of formation of 2%. This plaque has a melt index (I ₂ ) (ASTM D-1238,
230 ° C., 2.16 kg) at 11.49 decigrams per minute (dg / min)
It is. When a three-point flex test (ASTM D-790) was performed, the test showed a flex modulus of 21293.5 psi (1511.9 MPa) and a secant modulus of 15
8680.9 psi (1094.1 MPa) is evident. Gloss test (AST
The results of MD-523) are 26.1, 55.0 and 96.9 at incident angles of 20 °, 60 ° and 85 °, respectively. Dynat tested at 23 ° C
The p total energy was scored 15.3 ft-lbs (ft-lbs) (20.7
4 joules (J)). The results of the Izod impact strength tests at 23 ° C and -30 ° C were 0.97 ft-lbs / in and 0.70 ft-lbs, respectively.
/ In. The weld line Izod impact strength at room temperature is 1.43 ft-l
bs / in. (3.0KJSM (Kiro Joules Square)
Meters)). The heat deformation at 66 psi (0.46 KPa) was 94
. 3 ° C.

Example 8-Preparation of TPO Example 7 is repeated using the EO copolymer prepared in a single reactor instead of the interpolymer used in Example 7. This EO copolymer is MV21, RR
16 and PRR 10.7. The resulting samples have a Shore D hardness at 1 and 10 seconds of 65.4 and 61.6, respectively. Tensile properties are tensile breaking strength 2
342 psi (16.1 MPa), ultimate elongation 146%, tensile strength 33 when formed
09 psi (22.8 MPa), and elongation at the time of formation of 8%. The tensile properties of the weld line are tensile strength at break 1983 psi (13.7 MPa), ultimate elongation 2%, tensile strength at the time of formation 1978 psi (13.6 MPa), and elongation at the time of formation 2%. This plaque has an I _{2 of} 11.49 dg / min. The flex modulus and the 2% secant modulus were 209944.0 psi (1447.
5 MPa) and 167938.0 psi (1157.9 MPa). The results of the gloss test were 51.5 at incident angles of 20 °, 60 ° and 85 °, respectively.
, 71.5 and 91.2. The Dynatup test tested at 23 ° C. has a score of 20.5 foot-lbs (ft-lbs) (27.8 J). The result of the Izod impact strength test at 23 ° C. was 2.39 ft-lbs / in (5.0K
JSM). The weld line Izod impact strength at room temperature is 1.82 ft-
lbs / in. (3.8 KJSM).

Examples 7 and 8, respectively, show that satisfactory TPE and TPO can be prepared using the interpolymers of the present invention. Other TPEs, TPOs and TPVs are suitably prepared in accordance with the teachings provided herein.

[0120] was added (Example 9-EAO polymer production) _{H 2} flow, except changing the variables and monomer repeating the process of Example 1 and 2, to produce the EO copolymers. The variables are as follows: C ₂ feed rate 30.4pph, _{C 8} feed rate 29.8pph, _{H 2} feed rate 10.6
sccm (0.0055 mol%), reactor temperature 102 ° C., first catalyst flow 0.65 p
ph, co-cat flow 0.35 pph, scav flow 0.69 pph, Cz conversion 8
9.8%, reactor pressure 475 psig (3.28 MPa), catalyst efficiency 0.78 MM
# / #, Cocat / Ti molar ratio 4, and Scav / Ti molar ratio 5.54. The resulting polymer was MV21.4, RR16, PRR10.7, MW12030
0 and MWD 2.6.

[0121] Similar results to those obtained in Examples 1-9 are all expected with the other catalysts, cocatalysts, scavengers and process variables disclosed above.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08L 23/08 C08L 23/08 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU) , TJ, TM), AE, AL, AU, BA, BB, BG, BR, CA, CN, CR, CU, CZ, DM, EE, GD, GE, HR, HU, ID, I L, IN, IS, JP, KP, KR, LC, LK, LR, LT, LV, MG, MK, MN, MX, NO, NZ, PL, RO, SG, SI, SK, SL, TR, TT , UA, US, UZ, VN, YU, ZA (72) Inventor Morgan Mark Hughes United States 77515 Texas Angleton Milton Street 708 (72) Inventor Michael Kenneth Ruffner United States 77566 Texas Lake North Road 1403 (72) Inventor Larry Alan Maisk United States of America 70820 Baton Rouge Bell Fountain Court, Louisiana 5223 (72) Inventor Deepak Radikal Parish Co., Ltd. 77566 Texas Lake Jackson North Trillium Court 59 F-term (reference) 4F071 AA15X AA20 AA21 AAAAAAE AE05 AE09 AE17 AF11 AH12 AH17 AH19 BA01 BB05 BB06 BB13 4J002 BB05W BB12X BB14X BB15W BB15X FD016 FD027 FD039 FD098 FD149 FD209 FD329 GJ01 GM00 GN00 GQ00 4J028 AA01A AB01A AC19A AC20A BA00A BA01B BB00B BC12B EB02 EB03 EB05 EB07 EB08 EB09 EB10 EB11 EB12 EB13 EB17 EB18 EB21 EC02 EC03 EC04 EC05 EC06 EC07 FA02 GA06 4J100 AA02P AA03Q AA04Q AA07Q AA16Q AA17Q AA19Q AB02Q AB04Q AR11R AR22S AS01R AS01S AS02R AS04R CA04 CA05 CA06 DA04 DA09 FA10 FA19 JA28 JA43 4J128 AA01 AB01 EB EB EB EB EB EB EB EB EB 00EB EB EB EB EB EB EB EB EB EB EB 00A EB18 EB21 EC02 EC03 EC04 EC05 EC06 EC07 FA02 GA06

Claims (25)

[Claims] 1. A shear-thinning ethylene / α-olefin interpolymer, wherein the interpolymer is a polymerized ethylene, at least one α-olefin.
-Characterized by having an olefin monomer and, optionally, at least one diene monomer therein, and having a processing rheological ratio (PRR) of at least 4,
The PRR = (interpolymer viscosity measured at 190 ° C. at a shear rate of 0.1 rad / sec) / (interpolymer viscosity measured at 190 ° C. at a shear rate of 100 rad / sec) + [3.82-interpolymer Mooney viscosity (ML) _{1 + 4} $ 1
25 ° C.)] × 0.3. 2. The method according to claim 1, wherein the interpolymer comprises (a) 90:10 to 10:90.
Wherein the α-olefin is a C _3-20 α-olefin and (b) a diene in the range of 0 to 25 weight percent based on the weight of the interpolymer. 2. The interpolymer according to claim 1, having a monomer content. 3. The interpolymer of claim 1, wherein the interpolymer has a Mooney viscosity (ML _{1 + 4} at 125 ° C.) in the range of 0.5 to about 200. 4. The method of claim 1, wherein the interpolymer has a molecular weight distribution (M
(w / Mn). 5. The interpolymer of claim 4, wherein said molecular weight distribution is at least 2.5 and said PRR is at least 8. 6. The interpolymer of claim 1, wherein the interpolymer is an EAODM interpolymer having a molecular weight distribution of at least 2.3, a Mooney viscosity (ML _{1 + 4} at 125 ° C.) of at least 15 and a PRR of at least 20. Interpolymer. 7. An ethylene / octene copolymer wherein said interpolymer has a molecular weight distribution of at least 2.3 and a Mooney viscosity (ML _{1 + 4} at 125 ° C.) of at least 5.
2. The interpolymer according to claim 1, wherein the interpolymer is one copolymer. 8. The group of alpha-olefins comprising propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1, styrene, p-methylstyrene and mixtures thereof. Wherein the optional diene monomer is 5-ethylidene-2-norbornene, 5-vinylidene-
2-norbornene, 5-methylene-2-norbornene, 1,4-hexadiene,
1,3-pentadiene, 7-methyl-1,6-octadiene, 1,3-butadiene, 4-methyl-1,3-pentadiene, 5-methyl-1,4-hexanediene, 6-methyl-1,5 3. The interpolymer according to claim 2, wherein the interpolymer is selected from the group consisting of heptadiene and mixtures thereof. 9. The composition of claim 1, further comprising a PRR promoting amount of an additional diene monomer, wherein the additional diene monomer is selected from the group consisting of dicyclopentadiene, norbornadiene, 1,7-octadiene, and 1,9-decadiene. The interpolymer according to claim 2, which is selected. 10. The method of making an ethylene / α-olefin interpolymer of claim 1, wherein the method comprises subjecting the ethylene, at least one ethylene, under conditions sufficient to achieve at least 60 weight percent ethylene conversion. Contacting an α-olefin monomer and optionally at least one diene monomer with a catalyst and an activating cocatalyst, wherein said conditions comprise a temperature of at least 70 ° C. and optionally
Comprising in the presence of an effective amount of hydrogen, wherein said amount is sufficient to maintain an interpolymer PRR of at least 4, and wherein said catalyst is a geometrically constrained metal complex. Manufacturing method. 11. The hydrogen content is 0% based on the sum of the total monomer content and the hydrogen content.
11. The method of claim 10, wherein the mole percentage is greater than but less than 0.10 mole percent. 12. The hydrogen content is 0% based on the sum of the total monomer content and the hydrogen content.
11. The method of claim 10, wherein the molar percentage is greater than but less than 0.05 molar percent. 13. The catalyst according to claim 1, wherein the catalyst is (t-butyl-amide) -dimethyl (η ⁵ -2).
-Methyl-s-indacen-1-yl) silane-titanium (IV) dimethyl,
(T-butylamido) - dimethyl - (eta ^5-2-methyl -s- indacene-1-
Yl) silanetitanium (II) 1,3-pentadiene, and (t-butylamido) dimethyl - (eta ^5-2-methyl -s- indacene-1-yl) silane - titanium (II) 2,4-hexadiene or (t -Butylamide) -dimethyl (
eta ^{5-2,3-dimethyl} indenyl) silane titanium (II) 1,4-diphenyl-1,3-butadiene, (t-butyl - amide) - dimethyl (eta ^5-2,3
The process according to claim 10, characterized in that it is selected from the group consisting of -dimethyl-s-indacen-1-yl) silanetitanium (IV) dimethyl and group B catalysts selected from mixtures thereof. 14. The method of claim 10, wherein said activating cocatalyst is trispentafluorophenylborane. 15. The interpolymer having an ethylene content of 20 to 95 weight percent (wt%), an α-olefin content of 80 to 5 wt%, wherein the α-olefin is a C _3-20 α-olefin, optionally The method of claim 10, having a diene monomer content ranging from 0 to 25 weight percent, all of the percentages being based on interpolymer weight and totaling 100 wt%. 16. The method of claim 10, wherein said interpolymer is amorphous. 17. The method of claim 10, wherein said interpolymer is at least partially crystalline, said temperature is at least 80 ° C., and said ethylene conversion is at least 80%. 18. An article of manufacture wherein at least a portion is formed from a composition comprising the interpolymer of claim 1. 19. The article is selected from the group consisting of wire and cable components, electrical insulation, belts, hoses, tubes, gaskets, membranes, moldings, extruded parts, automotive parts, adhesives, tire walls and tires. The article of claim 18, wherein: 20. The composition further comprising at least one selected from the group consisting of fillers, fibers, plasticizers, oils, colorants, stabilizers, foaming agents, setting retarders, setting accelerators, and crosslinking agents. 19. Article according to claim 18, comprising one additive. 21. The composition comprising more than 50 parts by weight of the crystalline polyolefin resin and less than 50 parts by weight of the interpolymer of claim 1, wherein the total amount of the crystalline polyolefin resin and the interpolymer is 100 parts by weight. A polymer blend composition characterized by: 22. The composition comprises from 60 to less than 10 parts by weight of a crystalline polyolefin resin and from 40 to more than 90 parts by weight of the interpolymer of claim 1, wherein the interpolymer is based on the weight of the interpolymer. A thermoplastic vulcanizing composition characterized in that it is at least partially crosslinked so as to have a gel content of at least 70% and the total amount of crystalline polyolefin resin and interpolymer is 100 parts by weight. 23. The crystalline polyolefin resin is a polypropylene homopolymer, propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 1-hexene,
A copolymer of an α-olefin selected from the group consisting of octene, 2-methyl-1-propane or 4-methyl-1-pentene, or a blend of a polypropylene homopolymer and a propylene / α-olefin copolymer or a mixture thereof. 23. The composition according to claim 21, wherein 24. The composition according to claim 23, wherein said α-olefin is ethylene. 25. An article of manufacture formed from the composition of any one of claims 21 to 24.